ISOLATION O F DEACETYLVIGUIESTENIN AND ERIOFLORIN FROM HELIAiVTHUS TUBEROSUS H. h t O R I M O T 0 T h e Graduate School of Food and Medicinal Sciences, Kobe-Gakuin Cniversity, Tarumi-ku, K o b e , 673, J a p a n and
H . OSHIO Central Research Division, Takeda Chemical Industries, Ltd., Yodogawa-ku, Osaka, 532, J a p a n
deacetylviguiestenin on hydrogenation. The rotation of 3 was significantly close to that of erioflorin reported by Torrance et al. (3). These findings show that the structure of 3 coincides n-ith erioflorin.
In the previous papers (I), the authors elucidated the structure of heliangine (l), a plant growth regulator isolated from H e l i a d z u s tuberosus L. (Compositae) by Shibaoka (2). Recently, we have isolated two other heliangolides (2 and 3) from the same plant. The 'H nmr, nmr spectra and optical rotation of 2 indicated that it was deacetylviguiestenin (tagitinin E) (3, 4). The 'H nmr spectrum of 2 was superimposable upon that of an aut hentic sample. It was deduced that 3 was also a heliangolide containing a methacrylate moiety from its 'H nmr and 13C nmr spectra; 3 afforded 11,13-dihydro-
TABLE.
l3C nmr d a t a of heliangolides in CDC1, ( 6 ) .
Comp. 2
C-atom
1
3
-~
1. . . . . . . . . . . . . . .
60.6
60.5
60.5
3 . . . . . . . . . . . . . . . 72.0 4 . . . . . . . . . . . . . . . 141.5 7 . .. . . . . . . . . . . . .
8.... . . . . . . . . . . . 9. . . . . . . . . . . . . .
48.4 76.1 43.5
12 . . . . . . . . . . . . . . . 169.4 13 . . . . . . . . . . . . . . . 124.5 14 . . . . . . . . . . . . . . . 1 9 . 7 15 . . . . . . . . . . . . . . . 2 2 . 9 1'. . . . . . . . . . . . . . 166.4 2' . . . . . . . . . . . . . . 127.6 3 ' . . . . . . . . . . . . . 138.7 4 ' . .. . . . . . . . . . . . 11.8 5'. . . . . . . . . . . . . . 14.5
0
!
74.0 74.1 48.2 48.2 75.5 76.5 43.8 43.4 58.6 58.6 137.2 137.1 169.3 169.3 124.5 1 124.6 19.9 19.6 22.9 22.8 1 7 5 . 6 165.7 34.1 135.1 18.9' 126.6
"Assignments are interchangeable.
EXPERIJIENTAL leaves of Heliunthus tuberosus L. (43 kg), collected a t Fukuchiyama Experimental Farm, Takeda Chemical Ind., in September 1975, were extracted with methanol for 4 days. After concentration in uaczm, t h e extract was mixed with water, methanol and hexane, then the lower layer was concentrated until organic solvent was evaporated. The aqueous solution was extracted RTith chloroform. The chloroform extract (76 g) was chromatographed over silica gel and eluted with chloroform-methanol ( 9 : l ) t o afford a mixture of heliangolides (22.4 9). From the methanol solution of this mixture, rrystals of 1 (10.8 g) were precipitated. ISOLATIOX O F HELI.ISGOLIDES.-DTy
4
0 3 R= 4'
748
Soy-Dee 19811 Norimoto & Oshio : Deacetylviguieqtenin & Erioflorin T h e mother liquor was chromatographed over silica gel, impregnated previously with glycerol (lo$), and eluted with chloroform t o give 1 (2.2 g) and a mixture of 1, 2 and 3 (3.8 9 ) . T h e l a t t e r misture (2.2 g) was chromatographed repeatedly through Sephad e s LH-20 column and eluted with hesanechloroform-ethanol (4:5:1) t o afford 1 (310 m g ) , 2 1273 mg) and 3 1769 mgj. HELIASGISE(1 ).-Recrystallization from methanol gave colorless needles, m p 240243" (6). It was identical with an authentic sample (mmp, ir and 1H nmr spectra). DE.ICETTL\IGTIESTESIS121 .-Recryst allization from methanol gave colorless nkedles, mp 218-219": [ ~ r ] ~ ~ ~ -ICHC1,): 9 9 ; ~ ir IKBr) 34.50 (OH,, 1750 (lacrone), 1730 (esterj, 1680 cm-1 ( C = C ] : 'H nmr (CDC13) 6 1.11 iGH, d, J = 7 0 Hz, 3'-H and 4'-Hi. I t was identical 41th an authentic sample ('H nmr spectrum I
ERIOFLORIS (3) -Recrjstallization from methanol gave colorless needles, mp 22i230". [ 2oD-11TC (CHCls). ir 1KBr) 3420 (OH), 4]7X (lactone), 1708 (ester), 1660, 1630 em-' I C = C ) . lH nmr (CDC13) 6 1.89 (3H, broad s, 4'-H), 5 57 ( l H , m, 3'-H), 6.08 ( l H , m, 3'-H). H I - D R O G E S I T I O S OF 3 TO 11,13-DIHTDRDD E A C E T T L ~ I G ~ I E S T E ~ I S . - C o m p o U n d3 1159
mg) in methanol was hydrogenated over 5s Pd-C until 2 mol of hydrogen was taken-up.
749
T h e product gave colorless prisms, m p 191192", (100 mg) on recrystallization from methanol. I t was identical with 11,13dihydrodeacetylviguiestenin (mmp, i r and 1H nmr spectra). .ICKSOWLEDGMEXTS We are grateful t o Dr. W. Herz for 'H nmr chart of deacetylviguiestenin and valuable suggestions for structure determination. T h e authors also thank Mr. F. Kawanishi, Fukuchiyama Exp. F a r m of Takeda Chemical I n d . , for collection of plant materials. Recei;,ed 24 February 1981
L I T E R A I T L Y R EC I T E D 1. H . Morimoto, T.Sanno and H. Oshio, Tetrahedron, 22, 3173 (1966); 31. Xishikawa, K. Kamiya, rl. T a k a b a t a k e , H. Oshio. T.Tomiie and I . X i t t a . ibid.. 22, 3601 (1966). 2. H . Shibaoka, P l a n t and Cell Phgsiol., 2, 175 (1961). 3. P. K. Chowdur?-, S . C. Barua, R . P. Sharma, G . Thyagarajan and W. Herz, J . Orp. Chenz.. 45. 535 11980). 4. R . PA and R . ' P . Rastogi, Ind. J . Chem., K B , 533 (1977). 5 . S. J . Torrance, T. A. Geissman and LI. R . Chedekel, Phsfochemzstri',8 , 2381 (19691. 6. R e wish t o correct t h e mD of helianeine (1) cited in lit. 1 (227-229").
-
